Download PDF
Synthesis 2012(4): 628-634  
DOI: 10.1055/s-0031-1290155
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective Total Synthesis of (+)- and (-)-Vittatalactone

Jhillu Singh Yadav*a,b, Eedubilli Srinivasa, Chinta Krinda Suresh Kumara, Ahmad Al Khazim Al Ghamdib
Natural Product Chemistry, Organic Chemistry Division-I, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 607, India
Fax: +91(40)27100387; e-Mail: yadavpub@iict.res.in;
Engineer Abdullah Baqshan for Bee Research, King Saud University, Riyadh, Saudi Arabia
Further Information

Publication History

Received 4 November 2011
Publication Date:
25 January 2012 (online)

    Permissions and Reprints All articles of this category

Abstract

The asymmetric total synthesis of both enantiomers of (+)- and (-)-vittatalactone has been achieved using a desymmetrization strategy to create three methyl chiral centers. The key steps in these total syntheses are Myers asymmetric alkylation, copper-­catalyzed alkylation, 2,2,6,6-tetramethyl-1-piperidinyloxyl-(diacet­oxyiodo)benzene [TEMPO-PhI(OAc2)] promoted oxidation and p-toluenesulfonyl chloride mediated lactonization. The products are obtained in good overall yields employing linear synthetic sequences.

Key words

vittatalactone - desymmetrization - Myers asymmetric alkylation - copper-catalyzed alkylation - lactonization

3

Initially, we attempted the total synthesis of (+)-vittatalactone according to the structure proposed by Francke;¹ however, the optical rotation of our synthetic sample did not match that reported. Thus we started to synthesize the opposite isomer. Whilst this work was in progress, Breit and co-workers assigned the relative and absolute stereochemistry of (+)-vittatalactone and its stereoisomer. The spectral data we had obtained earlier were in good agreement with those reported by Breit et al. for (-)-vittatalactone.